Removal Of Copper From Water Using Columns Experiment Of Lignite, Shale, And Ironsand | Boreborey | Journal of Applied Geology 7193 12554 1 PB
J. SE Asian Appl. Geol., Jan–Jun 2012, Vol. 4(1), pp. 22–28
REMOVAL OF COPPER FROM WATER USING
COLUMNS EXPERIMENT OF LIGNITE, SHALE,
AND IRONSAND
Ty Boreborey,∗ Wahyu Wilopo, and Doni Prakasa Eka Putra
Department of Geological Engineering, Gadjah Mada University, Yogyakarta, Indonesia
Abstract
shown to be negative which showed an increasing of
Cu2+ in natural ironsand into solution.
Keywords: Copper, ironsand, shale, lignite, column experiment
Experimental studies using column testing of lignite, shale, and ironsand in copper solution were
carried out to determine the adsorption capacity of
lignite, shale, and ironsand in remediation of water
contaminated with copper. Lignite, shale, and ironsand were analyzed using XRD, SEM/EDX, and
XRF. The treatment process by column adsorption
was carried out over a period of 24 hours at a stable velocity of 0.005ml/s. After treatment, the remaining copper in the solution was recorded, thus
allowing the adsorption capacity of lignite, shale,
and ironsand to be calculated. The results revealed
that when the solution was treated by lignite and
shale there was a good degree of copper removal,
while the ironsand had very poor degree of copper
removal. The best material for copper removal was
lignite with 25-mesh grain size. Pyrite, graphite,
calcite, and illite were found in lignite and smectite, calcite, pyrite, hematite, and illite were found
in shale. These materials were also shown to contain
an abundance of high-valence elements in Al2 O3 ,
SiO2 , and Fe3 O4 which contributes to additional adsorption capacity. CAC values for lignite and shale
reached nearly to 100%, suggesting that lignite and
shale have a high adsorption capacity. In contrast,
ironsand, which has mostly sand minerals with little clay and organic content, caused the pollutant to
move rapidly to the water table, reducing the adsorption potential. CAC values treated by ironsand were
1
Introduction
Introduction Water can be contaminated by
heavy metals which include copper derived
from various sources. Heavy metal contamination of groundwater is a widespread problem in
Indonesia. The primary sources of copper in industrial wastewaters are metal-process pickling
baths and plating baths. In general, copper is
soluble and bio available at low pH and therefore toxicity problems are likely to be more severe in acid environments (Allowey and Ayres,
1993). Many techniques have been proposed for
removing contaminants from water, although
most of them suffer from particular technical
and economic limitations (Batchelor et al, 2002).
Column and bach tests have been carried out on
groundwater with known contamination levels
of metals in laboratory conditions using variable concentrations of contaminants and reactive materials (Freethey et al, 2002).
The objective of this research was to characterize the lignite, shale and ironsand in
terms of mineralogy, chemical composition,
and physical properties in their initial conditions. Through their characteristic we also
want to know the cation adsorption capacity
of lignite, shale and ironsand and to identify
the most effective adsorbent materials between
∗ Corresponding author: T. BOREBOREY, Department
of Geological Engineering, Faculty of Engineering, Gadjah
Mada University, Jl. Grafika 2 Yogyakarta, 55281, Indonesia. E-mail: ty.boreborey2@gmail.com
22
REMOVAL OF COPPER FROM WATER USING LIGNITE, SHALE, AND IRONSAND
Figure 1: Schematic diagram of the experimental set up for the adsorption process.
lignite, shale and ironsand in removing copper
ions from the water.
2
method of column adsorption was done by
putting the 300g of ironsand, lignite and shale
samples of 10-mesh and 25-mesh each into PVC
columns, then flowing vertically the solution of
copper with the concentrations of 7ppm into the
columns. The amount of the dry ironsand, lignite and shale grains requires only one experiment each with the two different grain sizes
done simultaneously over 24 hours, which is
considered enough to achieve equilibrium conditions at constant temperature (25◦ C). This is
to keep the materials in suspension and allow
the ion exchange reaction between the cations
of ironsand, lignite and shale with the Cu2+ in
solution. After the experiment, all the solutions
were analyzed by the AAS (atomic absorption
spectrometer) method to identify the remaining
copper. The formula of Vega et al (2005) to calculate the cation adsorption capacity (CAC) or
the concentrations of heavy metals adsorbed by
the ironsand, lignite and shale granular is expressed below:
Materials and Methods
CAC =
The goal of laboratory work was to determine
the characteristics of the adsorption materials
in terms of physical, mineralogical, and chemical properties. The lignite sample was taken
from Samigaluh Kulon Progo, the shale from
Bogor, and the ironsand from Glagah beach.
These three materials were first characterized
by means of X-ray diffraction (XRD) investigation, scanning electron microscope or energy dispersive X-ray (SEM/EDX), X-ray Fluorescence (XRF) and physical property analysis.
Secondly, the column adsorption experiments
were conducted over a period of 24 hours. A total of 6 columns were used with 6 cm diameters
and heights of 30cm each. Two different sizes
of grains were chosen for each sample, which
were coarse 10-mesh and fine 25-mesh and prepared in 300g samples for each material. The 6
samples were then put into different columns as
the reactive media. The solution of copper was
allowed to flow vertically through the column
at a constant velocity of 0.005ml/s (Figure 1).
The experiment on groundwater treatment
using lignite, shale, and ironsand with the
Ci − C f
or Cads = Ci − C f
Ci
(1)
Where:
CAC: cation adsorption capacity (percentage
adsorption)
Cads : concentration of heavy metal adsorbed
by iron sand, lignite, and shale
C i : initial concentration of heavy metal (before the experiment)
C f : final concentration of heavy metal (after
the experiment).
Figure 1: Schematic diagram of the experimental set up for the adsorption process
3
3.1
Results and Discussion
Lignite
The XRD and XRF analysis of the lignite sample
indicates that the sample contains several abundant mineral types such as pyrite, graphite,
and calcite (Figure 2, Table 1). The presence
of graphite reveals that lignite contains organic
matter that plays an important role in the adsorption mechanism. Meanwhile the presence
of pyrite, calcite, tourmaline, and some clay
c 2012 Department of Geological Engineering, Gadjah Mada University
23
BOREBOREY et al
Figure 2: X-ray diffractogram of the lignite sample.
Table 1: The result of specific major oxides and
trace metals for this research from XRF analysis
of lignite.
was absorbed by Al2 O3 and SiO2 which also
have abundant weights in lignite.
3.2
Shale
XRD analysis of the shale samples display the
major contents of smectite and calcite shown at
the peaks of the diffractogram (Figure 3). Moreover, illite, hematite, and pyrite are also present
in the content.
The XRF analysis showed the specific major
oxides and trace metals of shale which included
SiO2 , Al2 O3 , Na2 O, CaO, K2 O, TiO2 , Cd, Cu, Fe,
Pb, Zn, Mn, and Ag (Table 2). We can see Fe2 O3 ,
SiO2 , and Al2 O3 are much more abundant than
other chemicals. This means the shale, like lignite, is suitable as an ion adsorption material.
mineral also contribute to an overall high adsorption capacity.
Using the weights of oxides present in the lignite sample, it may be interpreted that the presence of Fe2 O3 rose to 10.91, meaning some copper was co-precipitated in this oxide and some
24
3.3
Ironsand
From the XRD analysis of ironsand sample,
we can see some major contents of magnetite,
olivine, quartz, calcite, and albite show at the
peaks of the diffractogram (Figure 4). This material was show to lack clay and organic matter
so we could interpret which would suggest in
c 2012 Department of Geological Engineering, Gadjah Mada University
REMOVAL OF COPPER FROM WATER USING LIGNITE, SHALE, AND IRONSAND
Figure 3: X-ray diffractogram of the shale.
Table 3: The result of specific major oxides and
trace metals from XRF analysis of ironsand.
Table 2: The result of specific major oxides and
trace metals from the XRF analysis of shale.
theory that it would have a low adsorption capacity. The XRF analysis shows the major element oxides in the sample (Table 3).
3.4
Solution Copper Treatment
To know the adsorption capacity of the lignite,
shale, and ironsand samples for treating copper,
a study of physical and chemical characteristics was done. This study included pH, grain
c 2012 Department of Geological Engineering, Gadjah Mada University
25
BOREBOREY et al
Figure 4: X-ray diffractogram of the ironsand.
size, crystal structure and chemical composition analysis. Experimental data from copper
solutions from XRD and XRF analysis show that
Cu2+ was removed by shale and lignite more
than ironsand. The negative values from ironsand suggest that it is not suitable for the treatment copper whatsoever.
According to Figure 5, the CAC of shale of
grain size 25-mesh is nearly 100% from the beginning of treatment at the duration of 20 hours
at which point CAC began to drop. The CAC of
shale with grain size 10-mesh decreased at the
duration 18-24 hours. Lignite however strongly
absorbed Cu2+ over the entire period of treatment with no apparent decreasing of CAC even
at the duration of 24 hours. Ironsand displayed
negative values for CAC, and it can thus be said
that it has no capacity in copper removal and
may even more cause the content of Cu2+ in solution to increase.
26
4
Conclusion
The absorption capacities of lignite, shale and
ironsand have been characterized. For lignite,
XRD showed that clay minerals and the organic
matter were abundant and XRF showed abundant weights for the elements and oxides C,
Al, Si, Fe, Al2 O3 , SiO2 , and Fe3 O4 . In comparison, shale contained no organic content, but
more clay minerals were detected. XRF analyses showed abundant weight for the elements
and oxides Al, Si, Fe, Al2 O3 , and SiO2 . These
parameters play an important role in the degree
of overall adsorption. In contrast with lignite
and shale, ironsand analysis showed abundant
magnetite, olivine, quartz, and calcite and a
lack of clay and organic matter. This is thought
to cause ironsand to have a low absorption capacity and cause the pollutant move rapidly to
the water table, reducing the effectiveness of the
adsorption process.
When the copper solution was treated by
lignite, Cu2+ became insoluble in the solution
due to pH increasing from acidity to neutral
and Cu2+ was co-precipitated. According to its
c 2012 Department of Geological Engineering, Gadjah Mada University
Table 4: Summary of discussion on characterization of lignite, shale, and ironsand.
REMOVAL OF COPPER FROM WATER USING LIGNITE, SHALE, AND IRONSAND
c 2012 Department of Geological Engineering, Gadjah Mada University
27
BOREBOREY et al
Figure 5: Copper adsorbed by lignite, shale and ironsand.
characteristic study, lignite has a high adsorption capacity and this was further suggested by
the column experiment in which CAC treated
by lignite reached to 99.47%. When the copper solution was treated by shale, the increasing of pH to neutral caused Cu2+ to be coprecipitated. From AAS analyses, CAC reached
to nearly 100% and agreeing with the characteristic studies of shale, it suggested that it has a
high degree in adsorption capacity. When the
copper solution was treated by ironsand, high
acidity caused Cu2+ to be more soluble. Ironsand’s characteristic studies suggested that it
would have a very low ability in adsorption
capacity, and the negative value of CAC suggested clearly that ironsand has no ability in
adsorption capacity to remove Cu2+ from the
solution, and increases the Cu2+ concentration
from the natural conditions. Through our experimental studies, it has been suggested that
the best material for copper removal in contaminated water is lignite with 25-mesh grain size.
Acknowledgment
The writer would like thank to the Indonesian Government, who have encouraged and
28
supported the budget for this Master’s Thesis and publication. Special acknowledgement
is made to friends and colleagues, who have
helped, contributed data, given valuable discussion and suggestions during the preparation
of this publication.
References
Alloway, B.J., and Ayres D.C. (1993) Chemical Principle of Environmental Pollution. By the Alden
Press, Oxford ISBN 0-751400130, p. 116–140.
Batchelor, B., Hapka, M., Igwe, G., Jensen, R., McDevitt, M., Schultz, D., and Whang, J. (2002) Method
for Remediating Contaminated Soils. United
States Patent No. 6,492,572 B2. p. 17–23.
Freethey, G.W., Naftz, D.L., Rowland, R.C. and
Davis, J.A. (2002) Deep Aquifer Remediation
Tools: theory design and performance monitoring. Elsevier, San Diego, 539p.
Vega, J.L., Ayala, J., Loredo, J., and Garcia, I. J.
(2005) Bentonite as Adsorbent of Heavy Metals
Ions from Mine Waste Leachates: Experimental
Data. 9th International Mine Water Association
Congress (IMWAC), Oviedo, Spain, p. 603–609.
c 2012 Department of Geological Engineering, Gadjah Mada University
REMOVAL OF COPPER FROM WATER USING
COLUMNS EXPERIMENT OF LIGNITE, SHALE,
AND IRONSAND
Ty Boreborey,∗ Wahyu Wilopo, and Doni Prakasa Eka Putra
Department of Geological Engineering, Gadjah Mada University, Yogyakarta, Indonesia
Abstract
shown to be negative which showed an increasing of
Cu2+ in natural ironsand into solution.
Keywords: Copper, ironsand, shale, lignite, column experiment
Experimental studies using column testing of lignite, shale, and ironsand in copper solution were
carried out to determine the adsorption capacity of
lignite, shale, and ironsand in remediation of water
contaminated with copper. Lignite, shale, and ironsand were analyzed using XRD, SEM/EDX, and
XRF. The treatment process by column adsorption
was carried out over a period of 24 hours at a stable velocity of 0.005ml/s. After treatment, the remaining copper in the solution was recorded, thus
allowing the adsorption capacity of lignite, shale,
and ironsand to be calculated. The results revealed
that when the solution was treated by lignite and
shale there was a good degree of copper removal,
while the ironsand had very poor degree of copper
removal. The best material for copper removal was
lignite with 25-mesh grain size. Pyrite, graphite,
calcite, and illite were found in lignite and smectite, calcite, pyrite, hematite, and illite were found
in shale. These materials were also shown to contain
an abundance of high-valence elements in Al2 O3 ,
SiO2 , and Fe3 O4 which contributes to additional adsorption capacity. CAC values for lignite and shale
reached nearly to 100%, suggesting that lignite and
shale have a high adsorption capacity. In contrast,
ironsand, which has mostly sand minerals with little clay and organic content, caused the pollutant to
move rapidly to the water table, reducing the adsorption potential. CAC values treated by ironsand were
1
Introduction
Introduction Water can be contaminated by
heavy metals which include copper derived
from various sources. Heavy metal contamination of groundwater is a widespread problem in
Indonesia. The primary sources of copper in industrial wastewaters are metal-process pickling
baths and plating baths. In general, copper is
soluble and bio available at low pH and therefore toxicity problems are likely to be more severe in acid environments (Allowey and Ayres,
1993). Many techniques have been proposed for
removing contaminants from water, although
most of them suffer from particular technical
and economic limitations (Batchelor et al, 2002).
Column and bach tests have been carried out on
groundwater with known contamination levels
of metals in laboratory conditions using variable concentrations of contaminants and reactive materials (Freethey et al, 2002).
The objective of this research was to characterize the lignite, shale and ironsand in
terms of mineralogy, chemical composition,
and physical properties in their initial conditions. Through their characteristic we also
want to know the cation adsorption capacity
of lignite, shale and ironsand and to identify
the most effective adsorbent materials between
∗ Corresponding author: T. BOREBOREY, Department
of Geological Engineering, Faculty of Engineering, Gadjah
Mada University, Jl. Grafika 2 Yogyakarta, 55281, Indonesia. E-mail: ty.boreborey2@gmail.com
22
REMOVAL OF COPPER FROM WATER USING LIGNITE, SHALE, AND IRONSAND
Figure 1: Schematic diagram of the experimental set up for the adsorption process.
lignite, shale and ironsand in removing copper
ions from the water.
2
method of column adsorption was done by
putting the 300g of ironsand, lignite and shale
samples of 10-mesh and 25-mesh each into PVC
columns, then flowing vertically the solution of
copper with the concentrations of 7ppm into the
columns. The amount of the dry ironsand, lignite and shale grains requires only one experiment each with the two different grain sizes
done simultaneously over 24 hours, which is
considered enough to achieve equilibrium conditions at constant temperature (25◦ C). This is
to keep the materials in suspension and allow
the ion exchange reaction between the cations
of ironsand, lignite and shale with the Cu2+ in
solution. After the experiment, all the solutions
were analyzed by the AAS (atomic absorption
spectrometer) method to identify the remaining
copper. The formula of Vega et al (2005) to calculate the cation adsorption capacity (CAC) or
the concentrations of heavy metals adsorbed by
the ironsand, lignite and shale granular is expressed below:
Materials and Methods
CAC =
The goal of laboratory work was to determine
the characteristics of the adsorption materials
in terms of physical, mineralogical, and chemical properties. The lignite sample was taken
from Samigaluh Kulon Progo, the shale from
Bogor, and the ironsand from Glagah beach.
These three materials were first characterized
by means of X-ray diffraction (XRD) investigation, scanning electron microscope or energy dispersive X-ray (SEM/EDX), X-ray Fluorescence (XRF) and physical property analysis.
Secondly, the column adsorption experiments
were conducted over a period of 24 hours. A total of 6 columns were used with 6 cm diameters
and heights of 30cm each. Two different sizes
of grains were chosen for each sample, which
were coarse 10-mesh and fine 25-mesh and prepared in 300g samples for each material. The 6
samples were then put into different columns as
the reactive media. The solution of copper was
allowed to flow vertically through the column
at a constant velocity of 0.005ml/s (Figure 1).
The experiment on groundwater treatment
using lignite, shale, and ironsand with the
Ci − C f
or Cads = Ci − C f
Ci
(1)
Where:
CAC: cation adsorption capacity (percentage
adsorption)
Cads : concentration of heavy metal adsorbed
by iron sand, lignite, and shale
C i : initial concentration of heavy metal (before the experiment)
C f : final concentration of heavy metal (after
the experiment).
Figure 1: Schematic diagram of the experimental set up for the adsorption process
3
3.1
Results and Discussion
Lignite
The XRD and XRF analysis of the lignite sample
indicates that the sample contains several abundant mineral types such as pyrite, graphite,
and calcite (Figure 2, Table 1). The presence
of graphite reveals that lignite contains organic
matter that plays an important role in the adsorption mechanism. Meanwhile the presence
of pyrite, calcite, tourmaline, and some clay
c 2012 Department of Geological Engineering, Gadjah Mada University
23
BOREBOREY et al
Figure 2: X-ray diffractogram of the lignite sample.
Table 1: The result of specific major oxides and
trace metals for this research from XRF analysis
of lignite.
was absorbed by Al2 O3 and SiO2 which also
have abundant weights in lignite.
3.2
Shale
XRD analysis of the shale samples display the
major contents of smectite and calcite shown at
the peaks of the diffractogram (Figure 3). Moreover, illite, hematite, and pyrite are also present
in the content.
The XRF analysis showed the specific major
oxides and trace metals of shale which included
SiO2 , Al2 O3 , Na2 O, CaO, K2 O, TiO2 , Cd, Cu, Fe,
Pb, Zn, Mn, and Ag (Table 2). We can see Fe2 O3 ,
SiO2 , and Al2 O3 are much more abundant than
other chemicals. This means the shale, like lignite, is suitable as an ion adsorption material.
mineral also contribute to an overall high adsorption capacity.
Using the weights of oxides present in the lignite sample, it may be interpreted that the presence of Fe2 O3 rose to 10.91, meaning some copper was co-precipitated in this oxide and some
24
3.3
Ironsand
From the XRD analysis of ironsand sample,
we can see some major contents of magnetite,
olivine, quartz, calcite, and albite show at the
peaks of the diffractogram (Figure 4). This material was show to lack clay and organic matter
so we could interpret which would suggest in
c 2012 Department of Geological Engineering, Gadjah Mada University
REMOVAL OF COPPER FROM WATER USING LIGNITE, SHALE, AND IRONSAND
Figure 3: X-ray diffractogram of the shale.
Table 3: The result of specific major oxides and
trace metals from XRF analysis of ironsand.
Table 2: The result of specific major oxides and
trace metals from the XRF analysis of shale.
theory that it would have a low adsorption capacity. The XRF analysis shows the major element oxides in the sample (Table 3).
3.4
Solution Copper Treatment
To know the adsorption capacity of the lignite,
shale, and ironsand samples for treating copper,
a study of physical and chemical characteristics was done. This study included pH, grain
c 2012 Department of Geological Engineering, Gadjah Mada University
25
BOREBOREY et al
Figure 4: X-ray diffractogram of the ironsand.
size, crystal structure and chemical composition analysis. Experimental data from copper
solutions from XRD and XRF analysis show that
Cu2+ was removed by shale and lignite more
than ironsand. The negative values from ironsand suggest that it is not suitable for the treatment copper whatsoever.
According to Figure 5, the CAC of shale of
grain size 25-mesh is nearly 100% from the beginning of treatment at the duration of 20 hours
at which point CAC began to drop. The CAC of
shale with grain size 10-mesh decreased at the
duration 18-24 hours. Lignite however strongly
absorbed Cu2+ over the entire period of treatment with no apparent decreasing of CAC even
at the duration of 24 hours. Ironsand displayed
negative values for CAC, and it can thus be said
that it has no capacity in copper removal and
may even more cause the content of Cu2+ in solution to increase.
26
4
Conclusion
The absorption capacities of lignite, shale and
ironsand have been characterized. For lignite,
XRD showed that clay minerals and the organic
matter were abundant and XRF showed abundant weights for the elements and oxides C,
Al, Si, Fe, Al2 O3 , SiO2 , and Fe3 O4 . In comparison, shale contained no organic content, but
more clay minerals were detected. XRF analyses showed abundant weight for the elements
and oxides Al, Si, Fe, Al2 O3 , and SiO2 . These
parameters play an important role in the degree
of overall adsorption. In contrast with lignite
and shale, ironsand analysis showed abundant
magnetite, olivine, quartz, and calcite and a
lack of clay and organic matter. This is thought
to cause ironsand to have a low absorption capacity and cause the pollutant move rapidly to
the water table, reducing the effectiveness of the
adsorption process.
When the copper solution was treated by
lignite, Cu2+ became insoluble in the solution
due to pH increasing from acidity to neutral
and Cu2+ was co-precipitated. According to its
c 2012 Department of Geological Engineering, Gadjah Mada University
Table 4: Summary of discussion on characterization of lignite, shale, and ironsand.
REMOVAL OF COPPER FROM WATER USING LIGNITE, SHALE, AND IRONSAND
c 2012 Department of Geological Engineering, Gadjah Mada University
27
BOREBOREY et al
Figure 5: Copper adsorbed by lignite, shale and ironsand.
characteristic study, lignite has a high adsorption capacity and this was further suggested by
the column experiment in which CAC treated
by lignite reached to 99.47%. When the copper solution was treated by shale, the increasing of pH to neutral caused Cu2+ to be coprecipitated. From AAS analyses, CAC reached
to nearly 100% and agreeing with the characteristic studies of shale, it suggested that it has a
high degree in adsorption capacity. When the
copper solution was treated by ironsand, high
acidity caused Cu2+ to be more soluble. Ironsand’s characteristic studies suggested that it
would have a very low ability in adsorption
capacity, and the negative value of CAC suggested clearly that ironsand has no ability in
adsorption capacity to remove Cu2+ from the
solution, and increases the Cu2+ concentration
from the natural conditions. Through our experimental studies, it has been suggested that
the best material for copper removal in contaminated water is lignite with 25-mesh grain size.
Acknowledgment
The writer would like thank to the Indonesian Government, who have encouraged and
28
supported the budget for this Master’s Thesis and publication. Special acknowledgement
is made to friends and colleagues, who have
helped, contributed data, given valuable discussion and suggestions during the preparation
of this publication.
References
Alloway, B.J., and Ayres D.C. (1993) Chemical Principle of Environmental Pollution. By the Alden
Press, Oxford ISBN 0-751400130, p. 116–140.
Batchelor, B., Hapka, M., Igwe, G., Jensen, R., McDevitt, M., Schultz, D., and Whang, J. (2002) Method
for Remediating Contaminated Soils. United
States Patent No. 6,492,572 B2. p. 17–23.
Freethey, G.W., Naftz, D.L., Rowland, R.C. and
Davis, J.A. (2002) Deep Aquifer Remediation
Tools: theory design and performance monitoring. Elsevier, San Diego, 539p.
Vega, J.L., Ayala, J., Loredo, J., and Garcia, I. J.
(2005) Bentonite as Adsorbent of Heavy Metals
Ions from Mine Waste Leachates: Experimental
Data. 9th International Mine Water Association
Congress (IMWAC), Oviedo, Spain, p. 603–609.
c 2012 Department of Geological Engineering, Gadjah Mada University